Water-insoluble azo-dyestuffs



-WATER-INSOLUBLE AZO-DXESTUFFS Panl'Rhyner, BaseLSWitzerIanQ'asslgnm-to r31 Ciba Limited, BaseL-Switzerland No-Drawing. Filed Dec. 2, 1958, Set. No. 777,582

Claimspriority, application "Switzerland 'Dec. 1-1, 1957 fi laim-s- (Cl. 260 20,7.*1)

in which A represents the radical of a 'diazo-component of the benzene series, and B represents a benzene radical containing in para-position to the azo-linkage an amino group in which one of the hydrogen atoms is replaced by a cyanethyl group and the other hydrogen atom by an alkyl group which may be substituted, and which :benzene radical contains an aliphatic acylamino .group in meta-position to the said amino group.

The invention also provides a process for the manufacture of the monazo-dyestufis of the above general formula, wherein a diazotized amine of the benzene series is coupled with a monamine of the benzene series capable of coupling in para-position to the amino group and in the amino group of which one hydrogen atom is replaced by a cyanalkyl group and the other hydrogen atom by an alkyl group which may be substituted, and which contains in meta-position .to the said amino group an aliphatic acylamino group, the said components being free from acid groups imparting solubility in water.

Of special interest are diam-components of the formula:

XQNH:

in which 'X, Y and Z veach represent a hydrogen atom or halogen atom or an alkyl, alkoxy, nitro, cyano, or alkyl-sulfone group. The term alkyl-sulfone group includes such groups substituted in the alkyl group such, for example, as chloromethyl-sulfone or fi-cyanethyl-sulfone groups.

As examples of suitable diazo-components there may be mentioned the following amines:

' lanaino-2-chlor-4-nitrobenzene,

1-amino-4-chlor-2-methyl-sulfonyl-benzene, 1-amino-2-chlor-4-methyl-sulfonyl-benzene, 1-amino 2-chlor-4-chlormethyl sulfonyl-benzene,

United States Patent 2,971,953 Patented Feb. 14, 1961 '2 1-amino-2-chlor-4-cyanethyl sulfonyl benzene, 1+amino-2z4-dicyanobenzene, 1-amino:2-cyano*4-methyl-sulfonyl benzene, 1-amino-4ecyano-2-methyl-sulfonylbenzene, l-amino-Z 4-bis- (methyl-sulfonyl) -.b enzene, 1-amino-2 6-dichloro-4-nitrobenzene, '1-amino-2:6-dibromoA-methyl-sulfonyl-benzene, lamin0-2-methyl-4-nitrobenzene, 1-amino-2-trifluoromethyl-4-nitrobenzene, l-amino-2-chlor-4 nitrobenzene, 1-amino-2-cyano=4-nitrobenzene, 1-amino-2-methyl sulfonyl-4-nitrobenzene, 1-amino-2-ch1oromethyl-sulfonyl 4rnitrobenzene, '1 aminoe2-cyanethylsulfonyl-4-nitrohenzene, 1-amino-2:4-dinitrobenzene, -1-amino'-2:4-dinitro-6tchlonbenzene, 1-amino-2:4-dinitro-6=brom benzene, l-amino-4-acetylaminobenzene.

As coupling components there may be mentioned more especiallyamines of the formula:

in which Acyl represents an aliphatic acyl group containing at most six carbon atoms, R represents an alkyl or hydroxy-alkyl group containing at most four carbon atoms, and R represents a hydrogen or halogen atom or an alkyl or alkoxy group containing at most four carbon atoms. As suitable acyl groups there may be mentioned more especially those of the formula -COC,, H in which n represents a whole number of at most 6. As examples there may be mentioned the radicals of formic acid, acetic acid, propionic acid, butyric acid and isobutyric acid. Finally, there may be mentioned as acyl groups semi-esters of carbonic acid, for example, the radicals of the formulae COOCH and COOC H s As examples of coupling components there may be mentioned:

- amino 3 propionylamino- The aforesaid coupling components can be obtained, for example, by nitrating N-alkyl-N-cyanethyl-benzenes in known manner in concentrated sulfuric acid, followed by reduction of the nitro group in the resulting N-alkyl- N-cyanalkyl-3-nitrobenzenes to the amino group and acylation of the latter group, or by reacting 1-amino-3- nitrobenzene with acrylonitrile to form N-cyanethylamino-3-nitrobenzene, reduction of the nitro group in the latter compound to the amino group and acylation of the latter group, whereby the N-cyanethylamino-3- 7b acylaminobenzene is obtained, which is converted by treatment with an alkyl halide, for example, ethylene chlorhydrin, into the N-hydroxyethyl-N-cyanethyl-3-acy1- aminobenzene. These coupling components can also be a 3 obtained by reacting N-acetyl-l:3 diamino-benzene with acrylonitrile to form N-acetyl-N'-B-cyanethyl-dian1inobenzene followed by alkylation to the N-acetyl -N flcyanethyl-N'-a1kyl-diaminobenzene.' i

The aforesaid diazo-components may be diazotized by methods in themselves known, for example, with the aid of a mineral acid, especially hydrochloric acid and sodium nitrite, or, for example, with a solution of nitrosylsulfuric acid in concentrated sulfuric acid.

The coupling can also be carried out by a method in itself known, for example, in a neutral to acid medium, if desired, in the presence of sodium acetate or like. butter substance influencing the speed of coupling or a catalyst, for example, pyridine or a salt thereof.

After the coupling reaction the dyestufis formed can easily be separated from the coupling mixtures, for example, by filtration, as the dyestuffs are practically insoluble in water.

The new monoazo-dyestufis of this invention are jexcellently suitable for dyeing or printing structures, for example, of polyamides, and especially fibers of cellulose acetate, artificial silk, cellulose triacetate or polyethylene terephthalate.

The dyeings produced with the new dyestuffs on the aforesaid structures are distinguished by the purity and brilliance of their tints and by their good general properties of fastness, especially their high fastness to sublimation and light.

The following examples illustrate the invention, the parts and percentages being by weight.

Example 1 13.8 parts of 1-amino-4-nitrobenzene are dissolved in 30 parts of water and 30 parts of concentrated hydrochlonic acid. After the addition of 80 parts of ice, 6.9 parts of sodium nitrite are added and the whole is stirred until the diazo-solution is clear and almost colorless.

The diazo-solution so obtained is run into a solution of 23.1 parts of N-ethyl-N-fl-cyanethyl-amino-3-acetylaminobenzene in 40 parts of 2 N-hydrochloric acid. The dyestuff is precipitated by the addition of a saturated solution of sodium acetate. Cellulose acetate artificial silk, nylon, cellulose triacetate and polyethylene terephthalate are dyed with the resulting dyestufif red tints which are fast to light and sublimation.

The N ethyl-N-cyanethylamino-3-'acetylaminobenzene j used as coupling component can be obtained as follows:

N-ethyl N-cyanethyl-aminobenzene is nitrated in known manner (see, for example, Organic Syntheses Col., volume 3, page 658 [1955]). In the resulting N-ethyl-N-cyanethyl-amino-3-nitrobenzene, the nitro group isreduced to 5 the amino group by a method in itself known and the amino group is acetylated by an ordinary method.

The coupling components used in the following examples can be obtained in an analogous manner.

Example 2 Example 3 16.3 parts of 1-amino-2-cyano-4-nitrobenzene are diazotized and'coupled with 23.1 parts of N-ethyl-N-p-cy- 'anethyl-amino-3-acetyl-amino-benzene in the manner described in Example 2. The resulting dyestufi dyes cellulose acetate, nylon, cellulose, triacetate, and polyethylene terephthalate claret red tints which are fastto light and sublimation.

Example 4 21.6 parts of 1-amino-4-nitrobenzene-2-methyl-sulfone are diazotized and coupled with 23.1 parts of N-ethyl-N-pcyanethylamino-3-acetylamino benzene and coupled. The resulting dyestutf dyes the aforesaid fibers blue-red tints of good fastness to light and sublimation.

Example 5 17.1 parts of 1-amino-benzene-4-methyl-sulfone, 25 parts of a 4 N-solution of sodium nitrite and 30 parts of ice in 40 parts of water are mixed with 25 parts of concentrated hydrochloric acid. The clear golden yellow diazo-solution is run slowly into 23.1 parts of N-ethyl-N- -cyanethylamino-3-acetylaminobenzene in 40 parts of 2 N- hydrochloric acid. By the addition of a solution of sodiumacetate the dyestufi is precipitated, and itdyes cellulose acetate, nylon, cellulose triacetate and polyethylene terephthalate yellow-orange tints.

Example 6 20.5 parts of 1-ami'no-2-ch1orobenzene-4-methyl-sulfone are diazotized and coupled with 23.1 parts of N-ethyl-N- ,5-cyanethyl-amino-3-acetylamino-benzene in the manner described in Example .2. The resulting orange dyestuif dyes the aforesaid fibers fast to light and sublimation. Further dyestuffs, which dye the aforesaid fibers the tints given in column 111 of the following table, are obtained by diazotizing the diazo-components -given in-column I, in the manner described in the preceding examples, and coupled with the coupling components given in column II.

I. Diem-component II. Coupling-component 1 Ill. T1111:

3 om NH, Q mm. NH ormcn t'zoocim T g V 4 can 7 r 2...... our m1,

1 NH 7 7 canon booms. t

r 01 s 2.....- our m1, g I 5 N HNB c'B -N V boocalii 1 gram of the dyestufi obtained as described in the first two paragraphs of Example 1 is pasted with 1.5 grams of sulfite cellulose waste liquor or dinaphthyl-methane disulfonic acid or a fatty alcohol, ethylene oxide condensation product, the paste is diluted with water to 4000 cc., and there are added, per liter, 1 cc. of acetic acid of 40% strength and 1 gram of a fatty alcohol-ethyleneoxide condensation product. 100 grams of a yarn of polyester fibers are dyed in the resulting dyebath for half to 1 hour at 115 to 132 C., whereby a deep red dyeing of very good fastness to light and sublimation is obtained.

What is claimed is:

1. Monoazo-dyestufis of the formula CHsOaS N=N N CHQCHQCN t wherein R represents an alkyl group having at most 2 carbon atoms and n represents a whole number of at most 4.

3. The monoazo-dyestufi of the formula 0 Hz 0 H1 ON NHCOCHs 4. The monoazo-dyestufi of the formula CH3 011 018 N=N N\ GHaCHrCN NHCOOH:

5. The monoazo-dyestufi of the formula NHCOCH:

6. The monoazo-dyestufi of the formula NHCO 04110 References Cited in the file of this patent UNITED STATES PATENTS Merian Ian. 23, 1959 

1. MONOAZO-DYESTUFFS OF THE FORMULA 